EP0504839A1 - Separation process of catalysts from suspensions by filtration - Google Patents

Separation process of catalysts from suspensions by filtration Download PDF

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Publication number
EP0504839A1
EP0504839A1 EP92104685A EP92104685A EP0504839A1 EP 0504839 A1 EP0504839 A1 EP 0504839A1 EP 92104685 A EP92104685 A EP 92104685A EP 92104685 A EP92104685 A EP 92104685A EP 0504839 A1 EP0504839 A1 EP 0504839A1
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EP
European Patent Office
Prior art keywords
filter elements
carboxylic acids
aryl
acid
filtration
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EP92104685A
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German (de)
French (fr)
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EP0504839B1 (en
Inventor
Ernst Ingo Dr. Leupold
Eduard Dr. Zeisberger
Manfred Kauffelt
Willi Dr. Herzog
Udo Dr. Dettmeier
Georg Dr. Weichselbaumer
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Hoechst AG
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Hoechst AG
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D29/00—Filters with filtering elements stationary during filtration, e.g. pressure or suction filters, not covered by groups B01D24/00 - B01D27/00; Filtering elements therefor
    • B01D29/11—Filters with filtering elements stationary during filtration, e.g. pressure or suction filters, not covered by groups B01D24/00 - B01D27/00; Filtering elements therefor with bag, cage, hose, tube, sleeve or like filtering elements
    • B01D29/31—Self-supporting filtering elements
    • B01D29/35—Self-supporting filtering elements arranged for outward flow filtration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D29/00—Filters with filtering elements stationary during filtration, e.g. pressure or suction filters, not covered by groups B01D24/00 - B01D27/00; Filtering elements therefor
    • B01D29/62—Regenerating the filter material in the filter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/08—Prevention of membrane fouling or of concentration polarisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2201/00—Details relating to filtering apparatus
    • B01D2201/08—Regeneration of the filter
    • B01D2201/085—Regeneration of the filter using another chemical than the liquid to be filtered
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/20—By influencing the flow
    • B01D2321/2008—By influencing the flow statically
    • B01D2321/2025—Tangential inlet

Definitions

  • the present invention relates to a process for separating suspended noble metal catalysts which are used in the production of ether carboxylic acids by catalytic oxidation of the corresponding ether alcohols with oxygen by filtration.
  • the task was therefore to develop a technically and economically viable method for separating catalysts from suspensions by filtration.
  • the present invention now relates to a process for separating noble metal catalysts which are used in the production of ether carboxylic acids by catalytic oxidation with a suspended catalyst, which is characterized in that cross-flow filtration is carried out and the filter elements used are subjected to a pretreatment and, if appropriate, an intermediate treatment subject to a medium which is not solid under the treatment conditions and consists of one or more carboxylic acids.
  • the catalyst-containing reaction mixture is pumped through the filter element tangentially to the membrane surface at a high overflow rate, the filtrate being discharged through the membrane layer transverse to the direction of flow, as described in detail in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume B2, pages 10- 54 is described.
  • Tubular filter elements with a membrane layer on the inside of the tubes are particularly suitable.
  • Preferred membrane and support materials are ceramic materials, ⁇ -Al2O3 and / or ZrO2. Plastic and carbon elements can also be used.
  • the membrane and support can be made of different materials.
  • the pore sizes required are expediently in the range which is customary for ultrafiltration, for example between about 1 and about 200 nm.
  • a suitable apartment is described in the example (cf. FIG. 1).
  • this is expediently immersed in the liquid carboxylic acid.
  • This can e.g. by filling the filter housing directly with the acid or after removing the filter in a separate container.
  • the treatment naturally takes place before the filtration process and is expediently repeated at certain intervals after a long period of operation. A repetition, which can take place after about 30 to 100 filtrations, for example, is not absolutely necessary; however, it can ensure long-term performance under extreme filtration conditions.
  • carboxylic acids are those of the general formula R-COOH, where R is a linear or branched hydrocarbon radical having 1 to 18 carbon atoms, which can be substituted by hydroxyl, alkoxy, carboxyl or halogen, such as fluorine, chlorine, bromine or iodine, or Aryl, alkyl (C1-C9) aryl or arylalkyl, for example the benzyl radical, where the aryl can each contain 6 to 16 carbon atoms, such as phenyl, naphthyl or biphenyl radicals, and can be substituted with the substituents mentioned.
  • R-COOH where R is a linear or branched hydrocarbon radical having 1 to 18 carbon atoms, which can be substituted by hydroxyl, alkoxy, carboxyl or halogen, such as fluorine, chlorine, bromine or iodine, or Aryl, alkyl (C1-C9) aryl or arylalkyl, for example the benzy
  • Carboxylic acids or mixtures or solutions of carboxylic acids which are liquid at the temperature at which the filter element is treated in particular aliphatic and aromatic compounds, such as formic acid, acetic acid, propionic acid, isovaleric acid, n-dodecanoic acid, benzoic acid and phenylacetic acid.
  • unsaturated, substituted or polybasic carboxylic acids such as glycolic acid, methoxyacetic acid, chloroacetic acid, lactic acid, crotonic acid, maleic acid, can also be used.
  • Acetic acid is preferred because of its good availability and ease of handling.
  • the treatment according to the invention is generally carried out at elevated temperature, preferably between approximately 30 and 250 ° C., particularly preferably between approximately 40 and 160 ° C. However, satisfactory results are still achieved even outside these limits.
  • the treatment time is generally chosen so that at least complete permeation of the filter is achieved.
  • An extension of the treatment time e.g. During an operational shutdown, over several days or weeks, the effectiveness of the filtering ability is not adversely affected.
  • the treatment can also be carried out with vaporous carboxylic acids, for example by passing the vapor over it.
  • a solution as obtained in the catalytic oxidation of ether carboxylic acids with a suspended catalyst consisting of 25 wt .-% ether carboxylic acid of the formula R- (OCH2CH2) n OCH2COOH, wherein R is linear alkyl groups with a distribution of C12 to C14 and n average value of 4, and 60% by weight of diethylene glycol dimethyl ether, 15% by weight of water and 5% by weight of a suspended commercially available catalyst (5% by weight of platinum on activated carbon) is hydrogenated at 80 ° C. for 30 minutes treated in a bubble column and then subjected to cross-flow filtration. Before use, the filter element is immersed in acetic acid at 70 ° C for 8 hours and then washed with water.
  • a suspended catalyst consisting of 25 wt .-% ether carboxylic acid of the formula R- (OCH2CH2) n OCH2COOH, wherein R is linear alkyl groups with a distribution of C12 to C14 and n average
  • FIG. 1 It consists of an Al2O3 tube (diameter: 7 mm, length: 250 mm), the inside of which consists of a membrane layer with pore sizes of 100 nm (10 ⁇ 9 m).
  • An apparatus according to FIG. 1 is used.
  • the solution is pumped at a linear flow rate of 5 m / s through the filter element (B) located in a housing (A).
  • the filtrate then flows at a speed of 2.0 l / h.
  • the catalyst can be concentrated to a solids content of approximately 30% by weight. This concentrate is returned to the catalytic oxidation.
  • the clear filtrate is processed further. Even after 200 filtrations with about 2000 l of filtrate, no decrease in the filtrate flow is observed.
  • An intermediate treatment acetic acid, 2 h, 70 ° C. is carried out after every 50 filtrations.

Abstract

Process for separating off noble metal catalysts which are used in the production of ether carboxylic acids by catalytic oxidation with a suspended catalyst, characterised in that cross-flow filtration is carried out and the filter elements used are pretreated with a medium, composed of one or more carboxylic acids, which is not solid under the treatment conditions. <IMAGE>

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Abtrennung von suspendierten Edelmetallkatalysatoren, die bei der Herstellung von Ethercarbonsäuren durch katalytische Oxidation der entsprechenden Etheralkohole mit Sauerstoff verwendet werden, durch Filtration.The present invention relates to a process for separating suspended noble metal catalysts which are used in the production of ether carboxylic acids by catalytic oxidation of the corresponding ether alcohols with oxygen by filtration.

Die katalytische Oxidation von Etheralkoholen gemäß der allgemeinen Gleichung

Figure imgb0001

ist seit längerem bekannt und beispielsweise in der DE-PS 29 36 123 und der EP-PS 206 054 beschrieben. Mit zunehmender Molmasse des Restes R wird jedoch die Abtrennung und damit die vollständige Wiedergewinnung und Rückführung des Edelmetallkatalysators schwieriger.The catalytic oxidation of ether alcohols according to the general equation
Figure imgb0001
has been known for a long time and is described, for example, in DE-PS 29 36 123 and EP-PS 206 054. With increasing molar mass of the radical R, however, the separation and thus the complete recovery and recycling of the noble metal catalyst becomes more difficult.

Es bestand daher die Aufgabe, ein technisch und wirtschaftlich tragbares Verfahren zur Abtrennung von Katalysatoren aus Suspensionen durch Filtration zu entwickeln.The task was therefore to develop a technically and economically viable method for separating catalysts from suspensions by filtration.

Gegenstand der vorliegenden Erfindung ist nun ein Verfahren zur Abtrennung von Edelmetallkatalysatoren, die bei der Herstellung von Ethercarbonsäuren durch katalytische Oxidation mit suspendiertem Katalysator verwendet werden, das dadurch gekennzeichnet ist, daß man eine Querstromfiltration durchführt und die eingesetzten Filterelemente einer Vor- und gegebenenfalls einer Zwischenbehandlung mit einem unter den Behandlungsbedingungen nicht festen Medium aus einer oder mehreren Carbonsäuren unterwirft.The present invention now relates to a process for separating noble metal catalysts which are used in the production of ether carboxylic acids by catalytic oxidation with a suspended catalyst, which is characterized in that cross-flow filtration is carried out and the filter elements used are subjected to a pretreatment and, if appropriate, an intermediate treatment subject to a medium which is not solid under the treatment conditions and consists of one or more carboxylic acids.

Bei der Querstromfiltration wird das katalysatorhaltige Reaktionsgemisch mit hoher Überströmgeschwindigkeit tangential zur Membranoberfläche durch das Filterelement gepumpt, wobei das Filtrat quer zur Strömungsrichtung durch die Membranschicht abgeführt wird, wie es im einzelnen in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Band B2, Seiten 10-54 beschrieben wird.In cross-flow filtration, the catalyst-containing reaction mixture is pumped through the filter element tangentially to the membrane surface at a high overflow rate, the filtrate being discharged through the membrane layer transverse to the direction of flow, as described in detail in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume B2, pages 10- 54 is described.

Besonders geeignet sind röhrenförmige Filterelemente mit einer Membranschicht auf der Innenseite der Röhren. Bevorzugte Membran- und Trägermaterialien sind keramische Materialien, α-Al₂O₃ und/oder ZrO₂. Kunststoff- und Kohlenstoffelemente können ebenfalls eingesetzt werden. Membran und Träger können aus verschiedenen Materialien bestehen. Die notwendigen Porengrößen liegen zweckmäßig im Bereich, der für eine Ultrafiltration üblich ist, beispielsweise zwischen etwa 1 und etwa 200 nm. Eine geeignete Appartur ist im Beispiel beschrieben (vgl. hierzu Figur 1).Tubular filter elements with a membrane layer on the inside of the tubes are particularly suitable. Preferred membrane and support materials are ceramic materials, α-Al₂O₃ and / or ZrO₂. Plastic and carbon elements can also be used. The membrane and support can be made of different materials. The pore sizes required are expediently in the range which is customary for ultrafiltration, for example between about 1 and about 200 nm. A suitable apartment is described in the example (cf. FIG. 1).

Bei der erfindungsgemäßen Behandlung des Filterelementes wird dieses zweckmäßig in die flüssige Carbonsäure getaucht. Dies kann z.B. durch direkte Füllung des Filtergehäuses mit der Säure oder nach Ausbau des Filters in einem separaten Gefäß erfolgen. Die Behandlung erfolgt naturgemäß vor dem Filtrationsvorgang und wird zweckmäßig nach längerer Betriebszeit in gewissen Abständen wiederholt. Eine Wiederholung, die beispielsweise nach etwa 30 bis 100 Filtrationen erfolgen kann, ist jedoch nicht zwingend erforderlich; sie kann jedoch bei extremen Filtrationsbedingungen die Leistungsfähigkeit über einen längeren Zeitraum sicherstellen.In the treatment of the filter element according to the invention, this is expediently immersed in the liquid carboxylic acid. This can e.g. by filling the filter housing directly with the acid or after removing the filter in a separate container. The treatment naturally takes place before the filtration process and is expediently repeated at certain intervals after a long period of operation. A repetition, which can take place after about 30 to 100 filtrations, for example, is not absolutely necessary; however, it can ensure long-term performance under extreme filtration conditions.

Als Carbonsäuren eignen sich insbesondere solche der allgemeinen Formel R-COOH, wobei R einen linearen oder verzweigten Kohlenwasserstoffrest mit 1 bis 18 Kohlenstoffatomen, der mit Hydroxy, Alkoxy, Carboxyl oder Halogen, wie Fluor, Chlor, Brom oder Jod, substituiert sein kann, oder Aryl, Alkyl (C₁-C₉)aryl oder Arylalkyl, z.B. der Benzylrest, wobei das Aryl jeweils 6 bis 16 Kohlenstoffatome enthalten kann, wie Phenyl-, Naphthyl- oder Biphenylreste, und mit den genannten Substituenten substituiert sein kann, bedeutet. Im allgemeinen eignen sich aber alleParticularly suitable carboxylic acids are those of the general formula R-COOH, where R is a linear or branched hydrocarbon radical having 1 to 18 carbon atoms, which can be substituted by hydroxyl, alkoxy, carboxyl or halogen, such as fluorine, chlorine, bromine or iodine, or Aryl, alkyl (C₁-C₉) aryl or arylalkyl, for example the benzyl radical, where the aryl can each contain 6 to 16 carbon atoms, such as phenyl, naphthyl or biphenyl radicals, and can be substituted with the substituents mentioned. In general, however, all are suitable

Carbonsäuren bzw. Gemische oder Lösungen von Carbonsäuren, die bei der Temperatur, bei der die Behandlung des Filterelementes vorgenommen wird, flüssig vorliegen, insbesondere aliphatische und aromatische Verbindungen, wie Ameisensäure, Essigsäure, Propionsäure, Isovaleriansäure, n-Dodecansäure, Benzoesäure und Phenylessigsäure. Es können aber auch ungesättigte, substituierte oder mehrbasische Carbonsäuren, wie Glykolsäure, Methoxyessigsäure, Chloressigsäure, Milchsäure, Crotonsäure, Maleinsäure, eingesetzt werden. Bevorzugt ist wegen der guten Verfügbarkeit und der einfachen Handhabbarkeit Essigsäure.Carboxylic acids or mixtures or solutions of carboxylic acids which are liquid at the temperature at which the filter element is treated, in particular aliphatic and aromatic compounds, such as formic acid, acetic acid, propionic acid, isovaleric acid, n-dodecanoic acid, benzoic acid and phenylacetic acid. However, unsaturated, substituted or polybasic carboxylic acids, such as glycolic acid, methoxyacetic acid, chloroacetic acid, lactic acid, crotonic acid, maleic acid, can also be used. Acetic acid is preferred because of its good availability and ease of handling.

Die erfindungsgemäße Behandlung erfolgt im allgemeinen bei erhöhter Temperatur, vorzugsweise zwischen etwa 30 und 250°C, besonders bevorzugt zwischen etwa 40 und 160°C. Auch außerhalb dieser Grenzen werden jedoch noch zufriedenstellende Ergebnisse erzielt.The treatment according to the invention is generally carried out at elevated temperature, preferably between approximately 30 and 250 ° C., particularly preferably between approximately 40 and 160 ° C. However, satisfactory results are still achieved even outside these limits.

Die Behandlungszeit wird im allgemeinen so gewählt, daß mindestens eine vollständige Permeation des Filters erreicht wird. Im allgemeinen ist eine Behandlungszeit von 0,5 bis 50 h, insbesondere 1 bis 10 h, ausreichend. Das Arbeiten unter erhöhtem Druck, beispielsweise bei 1 bis 10 bar, ist nicht erforderlich, kann aber wegen der schnelleren Permeation des Filters zur Verkürzung der erforderlichen Behandlungsdauer führen. Eine Verlängerung der Behandlungszeit, z.B. während eines Betriebsstillstandes, über mehrere Tage oder Wochen beeinflußt die Wirksamkeit der Filtrierfähigkeit nicht nachteilig. Die Behandlung kann auch mit dampfförmigen Carbonsäuren, beispielsweise durch Überleiten des Dampfes, durchgeführt werden.The treatment time is generally chosen so that at least complete permeation of the filter is achieved. A treatment time of 0.5 to 50 h, in particular 1 to 10 h, is generally sufficient. Working under increased pressure, for example at 1 to 10 bar, is not necessary, but can shorten the required treatment time due to the faster permeation of the filter. An extension of the treatment time, e.g. During an operational shutdown, over several days or weeks, the effectiveness of the filtering ability is not adversely affected. The treatment can also be carried out with vaporous carboxylic acids, for example by passing the vapor over it.

Überraschenderweise wird nach dem erfindungsgemäßen Verfahren das Problem der allmählichen Abnahme der Leistung der Filterelemente bei der Filtration, das z.B. bei der Filtration von langkettigen Ethercarbonsäuren, vor allem solcher mit Tensideigenschaften auftritt, durch eine technisch einfache Maßnahme gelöst.Surprisingly, the problem of the gradual decrease in the performance of the filter elements during filtration, which occurs, for example, in the filtration of long-chain ether carboxylic acids, especially those with surfactant properties, is solved by a technically simple measure.

Beispielexample

Eine Lösung, wie sie bei der katalytischen Oxidation von Ethercarbonsäuren mit suspendiertem Katalysator erhalten wird, bestehend aus 25 Gew.-% Ethercarbonsäure der Formel R-(OCH₂CH₂)nOCH₂COOH, worin R lineare Alkylgruppen mit einer Verteilung von C₁₂ bis C₁₄ bedeutet und n ein mittlerer Wert von 4 ist, sowie 60 Gew.-% Diethylenglykoldimethylether, 15 Gew.-% Wasser und 5 Gew.-% eines suspendierten handelsüblichen Katalysators (5 Gew.-% Platin auf Aktivkohle) wird 30 Minuten bei 80°C mit Wasserstoff in einer Blasensäule behandelt und anschließend einer Querstromfiltration unterworfen. Das Filterelement wird vor dem Einsatz 8 Stunden bei 70°C in Essigsäure getaucht und anschließend mit Wasser gewaschen. Es besteht aus einem Al₂O₃-Rohr (Durchmesser: 7 mm, Länge: 250 mm), dessen Innenseite aus einer Membranschicht mit Porengrößen von 100 nm (10⁻⁹ m) besteht. Es wird eine Apparatur gemäß Figur 1 verwendet. Die Lösung wird mit einer linearen Strömungsgeschwindigkeit von 5 m/s durch das in einem Gehäuse (A) befindliche Filterelement (B) gepumpt. Es wird ein Druck P₁ von 1,5 bar bei einer Temperatur von 70°C eingestellt. Das Filtrat strömt dann mit einer Geschwindigkeit von 2,0 l/h. Die Aufkonzentrierung des Katalysators gelingt bis zu einem Feststoffanteil von ca. 30 Gew.-%. Dieses Konzentrat wird in die katalytische Oxidation zurückgeführt. Das klare Filtrat gelangt zur weiteren Aufarbeitung. Auch nach 200 Filtrationen mit etwa 2000 l Filtrat wird noch kein Absinken des Filtratstroms beobachtet. Nach jeweils 50 Filtrationen wird eine Zwischenbehandlung (Essigsäure, 2 h, 70°C) durchgeführt.A solution as obtained in the catalytic oxidation of ether carboxylic acids with a suspended catalyst, consisting of 25 wt .-% ether carboxylic acid of the formula R- (OCH₂CH₂) n OCH₂COOH, wherein R is linear alkyl groups with a distribution of C₁₂ to C₁₄ and n average value of 4, and 60% by weight of diethylene glycol dimethyl ether, 15% by weight of water and 5% by weight of a suspended commercially available catalyst (5% by weight of platinum on activated carbon) is hydrogenated at 80 ° C. for 30 minutes treated in a bubble column and then subjected to cross-flow filtration. Before use, the filter element is immersed in acetic acid at 70 ° C for 8 hours and then washed with water. It consists of an Al₂O₃ tube (diameter: 7 mm, length: 250 mm), the inside of which consists of a membrane layer with pore sizes of 100 nm (10⁻⁹ m). An apparatus according to FIG. 1 is used. The solution is pumped at a linear flow rate of 5 m / s through the filter element (B) located in a housing (A). There is a pressure P₁ of 1.5 bar at a temperature of 70 ° C. The filtrate then flows at a speed of 2.0 l / h. The catalyst can be concentrated to a solids content of approximately 30% by weight. This concentrate is returned to the catalytic oxidation. The clear filtrate is processed further. Even after 200 filtrations with about 2000 l of filtrate, no decrease in the filtrate flow is observed. An intermediate treatment (acetic acid, 2 h, 70 ° C.) is carried out after every 50 filtrations.

Claims (9)

Verfahren zur Abtrennung von Edelmetallkatalysatoren, die bei der Herstellung von Ethercarbonsäuren durch katalytische Oxidation mit suspendiertem Katalysator verwendet werden, dadurch gekennzeichnet, daß man eine Querstromfiltration durchführt und die eingesetzten Fiiterelemente mit einem unter den Behandlungsbedingungen nicht festen Medium aus einer oder mehreren Carbonsäuren vorbehandelt.Process for the separation of noble metal catalysts which are used in the production of ether carboxylic acids by catalytic oxidation with a suspended catalyst, characterized in that cross-flow filtration is carried out and the filter elements used are pretreated with a medium which is not solid under the treatment conditions and consists of one or more carboxylic acids. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Carbonsäure die allgemeine Formel R-COOH hat, wobei R einen linearen oder verzweigten Kohlenwasserstoffrest mit 1 bis 18 Kohlenstoffatomen, der mit Hydroxy, Alkoxy, Carboxyl oder Halogen substituiert sein kann, oder Aryl, Alkyl(C₁-C₉)aryl oder Arylalkyl, wobei das Aryl jeweils 6 bis 16 Kohlenstoffatome enthalten kann und mit den genannten Substituenten substituiert sein kann, bedeutet.A method according to claim 1, characterized in that the carboxylic acid has the general formula R-COOH, where R is a linear or branched hydrocarbon radical having 1 to 18 carbon atoms, which may be substituted by hydroxy, alkoxy, carboxyl or halogen, or aryl, alkyl ( C₁-C₉) aryl or arylalkyl, where the aryl can each contain 6 to 16 carbon atoms and can be substituted with the substituents mentioned. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß als Carbonsäure Essigsäure eingesetzt wird.A method according to claim 2, characterized in that acetic acid is used as the carboxylic acid. Verfahren nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß man die Filterelemente mit einer oder mehreren Carbonsäuren zwischenbehandelt.Method according to one or more of claims 1 to 3, characterized in that the filter elements are treated with one or more carboxylic acids. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß man die Zwischenbehandlung nach etwa 30 bis 100 Filtrationen vornimmt.Process according to Claim 4, characterized in that the intermediate treatment is carried out after about 30 to 100 filtrations. Verfahren nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Filterelemente aus keramischem Material und/oder Kohlenstoff bestehen.Method according to one or more of claims 1 to 5, characterized in that the filter elements consist of ceramic material and / or carbon. Verfahren nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Filterlemente aus ZrO₂ und/oder α-Al₂O₃ bestehen.Method according to one or more of claims 1 to 6, characterized in that the filter elements consist of ZrO₂ and / or α-Al₂O₃. Verfahren nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß man die Filterelemente für 0,5 bis 50 h, insbesondere 1 bis 10 h, in die flüssige Carbonsäure taucht.Method according to one or more of claims 1 to 7, characterized in that the filter elements are immersed in the liquid carboxylic acid for 0.5 to 50 h, in particular 1 to 10 h. Verfahren nach einem oder mehreren der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß man bei erhöhter Temperatur, bevorzugt zwischen 30 und 250°C, insbesondere zwischen 40 und 160°C, arbeitet.Method according to one or more of claims 1 to 8, characterized in that one works at elevated temperature, preferably between 30 and 250 ° C, in particular between 40 and 160 ° C.
EP92104685A 1991-03-19 1992-03-18 Separation process of catalysts from suspensions by filtration Expired - Lifetime EP0504839B1 (en)

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DE4108870 1991-03-19

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999001206A1 (en) * 1997-06-30 1999-01-14 Basf Aktiengesellschaft Separation of suspended catalysts by cross-flow filtration on a membrane
WO2000003794A1 (en) * 1998-07-13 2000-01-27 Bucher-Guyer Ag Method and device for mixing fluids in a duct
DE102006057996A1 (en) * 2006-12-08 2008-06-12 Aquaworx Ag Filter module for filtering of particles in liquids, has two similar filter elements each downstream of first liquid outlet

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5490936A (en) * 1990-04-14 1996-02-13 Hoechst Aktiengesellschaft Process for catalyst recovery
DE4217245A1 (en) * 1992-05-25 1993-12-02 Degussa Process for the separation of catalyst-free working solution from the hydrogenation of the Anthrachionverfahrens for the production of hydrogen peroxide
US5955394A (en) * 1996-08-16 1999-09-21 Mobile Process Technology, Co. Recovery process for oxidation catalyst in the manufacture of aromatic carboxylic acids
AT405291B (en) * 1997-05-13 1999-06-25 Steirerbrau Ag METHOD FOR PRODUCING COLD-FILTERED BEER
US5919376A (en) * 1997-06-10 1999-07-06 Cae Ransohoff Inc. Filtration apparatus and method
US6533937B1 (en) * 1999-01-22 2003-03-18 Nitto Denko Corporation Methods of running and washing spiral wound membrane modules
US6432310B1 (en) * 1999-01-22 2002-08-13 Nitto Denko Corporation Methods of running and washing spiral wound membrane module
US6832652B1 (en) * 2003-08-22 2004-12-21 Bj Services Company Ultra low density cementitious slurries for use in cementing of oil and gas wells
US7174961B2 (en) * 2005-03-25 2007-02-13 Halliburton Energy Services, Inc. Methods of cementing using cement compositions comprising basalt fibers
US20070289917A1 (en) * 2006-06-15 2007-12-20 Mylin John M Separation system and method of operating
US7790646B2 (en) * 2007-12-20 2010-09-07 Chevron U.S.A. Inc. Conversion of fine catalyst into coke-like material
US7737068B2 (en) * 2007-12-20 2010-06-15 Chevron U.S.A. Inc. Conversion of fine catalyst into coke-like material
US20090159495A1 (en) * 2007-12-20 2009-06-25 Chevron U.S.A. Inc. Heavy oil conversion
US8722556B2 (en) * 2007-12-20 2014-05-13 Chevron U.S.A. Inc. Recovery of slurry unsupported catalyst
US8765622B2 (en) * 2007-12-20 2014-07-01 Chevron U.S.A. Inc. Recovery of slurry unsupported catalyst
ITUA20161506A1 (en) * 2016-03-09 2017-09-09 Della Toffola Spa METHOD AND IMPROVED PLANT OF TANGENTIAL FILTRATION

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3977967A (en) * 1973-05-10 1976-08-31 Union Carbide Corporation Ultrafiltration apparatus and process for the treatment of liquids
EP0052719A1 (en) * 1980-10-29 1982-06-02 MERCK PATENT GmbH Process for the separation of metal catalysts, and use of membrane separation apparatuses
US4895658A (en) * 1987-06-15 1990-01-23 The B. F. Goodrich Company Membrane cleaning compositions containing acrylic polymer

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1243507A (en) * 1968-03-13 1971-08-18 British Petroleum Co Ultrafiltration separation process
US4136025A (en) * 1977-08-18 1979-01-23 Ppg Industries, Inc. Method of cleaning membrane filter
DE2936123A1 (en) * 1979-09-07 1981-04-02 Hoechst Ag, 6000 Frankfurt METHOD FOR PRODUCING ALKOXY ACETIC ACIDS
US4311521A (en) * 1980-10-01 1982-01-19 Standard Oil Company (Indiana) Membrane separation of catalyst metals from trimellitic acid production and separation of cobalt from manganese
US4312778A (en) * 1980-10-01 1982-01-26 Standard Oil Company (Indiana) Membrane separation of catalyst metals from aromatic acid production
DE3522032A1 (en) * 1985-06-20 1987-01-02 Hoechst Ag METHOD FOR THE PRODUCTION OF CARBONIC ACIDS
US5102632A (en) * 1990-12-21 1992-04-07 Metallgesellschaft Aktiengesellschaft Two-step method for recovering dispersed noble metals

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3977967A (en) * 1973-05-10 1976-08-31 Union Carbide Corporation Ultrafiltration apparatus and process for the treatment of liquids
EP0052719A1 (en) * 1980-10-29 1982-06-02 MERCK PATENT GmbH Process for the separation of metal catalysts, and use of membrane separation apparatuses
US4895658A (en) * 1987-06-15 1990-01-23 The B. F. Goodrich Company Membrane cleaning compositions containing acrylic polymer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WORLD PATENTS INDEX Week 8005, Derwent Publications Ltd., London, GB; AN 80-08877C & SU-A-663 420 (BOR PRODN TRUST) *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999001206A1 (en) * 1997-06-30 1999-01-14 Basf Aktiengesellschaft Separation of suspended catalysts by cross-flow filtration on a membrane
WO2000003794A1 (en) * 1998-07-13 2000-01-27 Bucher-Guyer Ag Method and device for mixing fluids in a duct
DE102006057996A1 (en) * 2006-12-08 2008-06-12 Aquaworx Ag Filter module for filtering of particles in liquids, has two similar filter elements each downstream of first liquid outlet
DE102006057996B4 (en) * 2006-12-08 2011-08-25 Aquaworx Holding Ag filter module

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EP0504839B1 (en) 1995-03-01
CA2063324A1 (en) 1992-09-20
DK0504839T3 (en) 1995-07-24
DE59201487D1 (en) 1995-04-06
US5230804A (en) 1993-07-27
ES2072039T3 (en) 1995-07-01
ATE119065T1 (en) 1995-03-15
JPH0576779A (en) 1993-03-30

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